Metallocene compound, catalyst composition, olefin polymerization method and application

Abstract

The invention relates to the field of olefin polymerization, and discloses a metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and an application of the metallocene compound or the catalyst composition in olefin polymerization. The metallocene compound has a structure as shown in a formula (1), and in the formula (1), M is a tetravalent transition metal atom; x1 and X2 are respectively and independently a halogen atom, an alkyl group with a carbon atom number of 1-10, an aryl group with a carbon atom number of 6-12 or an N, N-dialkyl amino group with a carbon atom number of 2-8. The catalyst composition provided by the invention has the advantages of high catalytic activity, good copolymerization performance and high molecular weight of the obtained polymer. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of olefin polymerization, and in particular, to a metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and application of the metallocene compound or the catalyst composition in olefin polymerization. Background Art

[0002] Metallocene compounds for olefin polymerization have been a research hotspot in metal organic chemistry, catalysis, polymer chemistry and materials science in recent decades. Using this type of catalyst, olefin polymers with uniform molecular weight distribution and chemical composition distribution can be obtained, and the molecular structure and molecular weight of the polymer can be highly controllable by adjusting the catalyst structure. Metallocenes have strong copolymerization ability, which is reflected in two aspects (Chemistry Select 2020, 5, 7581–7585): on the one hand, under the same polymerization conditions, the content of comonomers in the copolymers obtained by metallocenes is higher than that of other catalysts, which is the high efficiency of their copolymerization; on the other hand, some monomers that cannot be catalyzed and polymerized by other catalysts can also be used as comonomers in the metallocene compound system, which is the broad spectrum of their copolymerization. Due to the high efficiency and broad spectrum of copolymerization, metallocene compounds can catalyze many new copolymers. Compared with copolymers obtained by other catalysts, these copolymers have new compositions and structures, and thus may have new properties, thereby realizing the application of polyolefin materials in new fields. For example, polyolefin elastomer (POE) is an industrialized high-end polyolefin material with broad applications in many aspects.

[0003] The structure of metallocene catalysts determines their catalytic performance. A small change in the structure may lead to a huge change in the catalytic performance. When designing metallocene catalysts, the polymerization activity and copolymerization performance of the catalyst, as well as the molecular weight of the polymer, will be improved as much as possible through structural design, thereby broadening the operating space of production and improving the economic efficiency of production.

[0004] Existing metallocene catalysts still have the problem of catalyst activity, copolymerization performance and polymer molecular weight needing to be improved. Summary of the invention

[0005] The purpose of the present invention is to provide a new metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the use of the metallocene compound or the catalyst composition in olefin polymerization. By using the catalyst composition of the present invention, the catalyst has the advantages of high catalytic activity, good copolymerization performance and high molecular weight of the obtained polymer.

[0006] In order to achieve the above object, the present invention provides a metallocene compound, wherein the metallocene compound has a structure shown in formula (1),

[0007]

[0008] In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0009] Preferably, M is a titanium atom, a zirconium atom or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a zirconium atom.

[0010] Preferably, X 1 and X 2 Each of them is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an N,N-dialkylamine group having 2 to 6 carbon atoms; more preferably, X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aromatic group having 6 to 8 carbon atoms, or an N,N-dialkylamino group having 2 to 6 carbon atoms; further preferably, X 1 and X 2 Each is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; more preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0011] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components:

[0012] a) the metallocene compound according to the first aspect of the present invention;

[0013] b) Co-catalyst component.

[0014] Preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound; more preferably, the co-catalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.

[0015] Preferably, the alkylaluminoxane is a compound selected from the structure represented by formula (2) and / or formula (3),

[0016]

[0017] In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n is an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n is an integer of 10 to 30.

[0018] Preferably, the alkylaluminoxane is methylaluminoxane.

[0019] Preferably, the organoboron compound is [B(C 6 F 5 ) 4 ] - Z + , Z + Having a structure represented by formula (4) or formula (5),

[0020]

[0021] Preferably, the organoaluminum compound is of the general formula AlX 1 X 2 X 3 The compound of the structure shown, X 1 , X 2 and X 3 are respectively a halogen atom or an alkyl group having 1 to 12 carbon atoms, X 1 , X 2 and X 3 They may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms.

[0022] Preferably, the organoaluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, preferably triisobutylaluminum.

[0023] Preferably, the co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated on the basis of aluminum is 1:(100-50000), preferably 1:(500-10000), and more preferably 1:(500-2000).

[0024] Preferably, the co-catalyst component is a combination of an organic boron compound and an organic aluminum compound, the molar ratio of the metallocene compound to the organic boron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), and the molar ratio of the metallocene compound to the organic aluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

[0025] According to a third aspect of the present invention, there is provided a method for olefin polymerization, wherein the method comprises contacting an olefin with the catalyst composition according to the second aspect of the present invention to carry out a polymerization reaction.

[0026] Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

[0027] Preferably, the olefin is ethylene or a combination of ethylene and an α-olefin.

[0028] Preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0029] Preferably, the partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0030] Preferably, the polymerization reaction is carried out in the presence of an organic solvent, and the organic solvent is one or more of toluene, cyclohexane and hexane.

[0031] Preferably, the polymerization reaction temperature is -50 to 200° C., and the polymerization reaction time is 1 to 300 minutes; more preferably, the polymerization reaction temperature is -20 to 150° C., and the polymerization reaction time is 5 to 60 minutes.

[0032] According to a fourth aspect of the present invention, there is provided use of the metallocene compound described in the first aspect of the present invention or the catalyst composition described in the second aspect of the present invention in olefin polymerization.

[0033] Through the above technical scheme, the present invention provides a new metallocene compound, a catalyst composition using the metallocene compound, an olefin polymerization method using the catalyst composition, and the use of the metallocene compound or the catalyst composition in olefin polymerization. By using the catalyst composition of the present invention, it has the advantages of high catalytic activity, good copolymerization performance and high molecular weight of the obtained polymer. DETAILED DESCRIPTION

[0034] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0035] The first aspect of the present invention provides a metallocene compound, wherein the metallocene compound has a structure shown in formula (1),

[0036]

[0037] In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0038] According to the metallocene compound of the present invention, in formula (1), M is a tetravalent transition metal atom, preferably, M is a titanium atom, a zirconium atom or a hafnium atom; more preferably, M is a titanium atom or a zirconium atom; particularly preferably, M is a zirconium atom.

[0039] According to the metallocene compound of the present invention, in formula (1), X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

[0040] Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0041] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Among them, methyl, ethyl, propyl, and isopropyl are preferred, and methyl or ethyl are more preferred.

[0042] Examples of the aromatic group having 6 to 12 carbon atoms include phenyl, benzyl, and phenethyl. Among them, benzyl is preferred.

[0043] In the present invention, preferably, in formula (1), X 1 and X 2 Each of them is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an N,N-dialkylamine group having 2 to 6 carbon atoms; more preferably, X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aromatic group having 6 to 8 carbon atoms, or an N,N-dialkylamino group having 2 to 6 carbon atoms; further preferably, X 1 and X 2 Each is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; particularly preferably, X 1 and X 2Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

[0044] In a particularly preferred embodiment of the present invention, X 1 and X 2 Same as Cl.

[0045] In another particularly preferred embodiment of the present invention, X 1 and X 2 The same is methyl.

[0046] In another particularly preferred embodiment of the present invention, X 1 and X 2 Same as benzyl.

[0047] In another particularly preferred embodiment of the present invention, X 1 and X 2 The same is N,N-dimethylamino.

[0048] As specific metallocene compounds, preferably the following compounds can be mentioned:

[0049] In formula (1), M is a titanium atom, X 1 and X 2 Same as Cl;

[0050] In formula (1), M is a titanium atom, X 1 and X 2 Same as methyl group;

[0051] In formula (1), M is a titanium atom, X 1 and X 2 Same as benzyl;

[0052] In formula (1), M is a titanium atom, X 1 and X 2 The same is N,N-dimethylamino;

[0053] In formula (1), M is a zirconium atom, X 1 and X 2 Same as Cl;

[0054] In formula (1), M is a zirconium atom, X 1 and X 2 Same as methyl group;

[0055] In formula (1), M is a zirconium atom, X 1 and X 2 Same as benzyl;

[0056] In formula (1), M is a zirconium atom, X 1 and X 2 The same is N,N-dimethylamino;

[0057] In formula (1), M is a hafnium atom, X 1 and X 2 Same as Cl;

[0058] In formula (1), M is a hafnium atom, X 1 and X 2 Same as methyl group;

[0059] In formula (1), M is a hafnium atom, X 1 and X 2 Same as benzyl;

[0060] In formula (1), M is a hafnium atom, X 1 and X 2 The same is N,N-dimethylamino.

[0061] The metallocene compound according to the present invention can be synthesized according to conventional methods in the art.

[0062] In the present invention, X 1 and X 2 The method for preparing a metallocene compound having an N,N-dialkylamine group having 2 to 8 carbon atoms preferably comprises the following steps:

[0063] 1) In the presence of a catalyst C and a first solvent, compound A and compound B are subjected to a first contact reaction to obtain an intermediate product D;

[0064] 2) in the presence of a second solvent, subjecting the intermediate product D to a second contact reaction with the compound E to obtain an intermediate product F;

[0065] 3) In the presence of a third solvent, the intermediate product F and M(NA 2 ) 4 A step of performing a third contact reaction to obtain compound H,

[0066]

[0067] Wherein, A is a hydrocarbon group having 1 to 4 atoms; n is an integer of 1 to 5; R 1 , R 2 , R 3 , R 4 Each is independently a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a tert-butyl group.

[0068] The following is a step-by-step explanation.

[0069] Step 1): In the presence of a catalyst C and a first solvent, compound A and compound B are reacted to form a first A contact reaction to obtain intermediate product D .

[0070] In the above step 1), in the catalyst C, n is preferably 2 or 3.

[0071] As the catalyst C, one or more of pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, piperidine and 2,2,6,6-tetramethylpiperidine are preferably used.

[0072] The amount of the catalyst C can be selected according to the compound A. Preferably, the molar ratio of the reactant A to the catalyst C is 1:1-5, more preferably 1:1.1-3.

[0073] In the above step 1), the first solvent is preferably methanol, more preferably anhydrous methanol.

[0074] The amount of the first solvent can be selected according to the compound A. For example, relative to 1 mol of the compound A, the amount of the first solvent can be 0.5-10 L, preferably 0.8-5 L, and more preferably 0.8-2 L.

[0075] In the above step 1), the amount of the compound B can be selected according to the compound A. Preferably, the molar ratio of the reactant A to the compound B is 1:1.2-10, more preferably 1:1.5-5, and further preferably 1:2-4.

[0076] In the above step 1), the contact method of the first contact reaction is not particularly limited, as long as the intermediate product D can be obtained. Preferably, the catalyst C is mixed with the first solvent and then subjected to the first contact reaction with the compound B.

[0077] The conditions of the first contact reaction may include: a temperature of 10-25° C. and a time of 8-90 h.

[0078] After the first contact reaction, the conventional refining method in the art can be used for refining. In a preferred embodiment of the present invention, after the first contact reaction is completed, the first contact reaction product is subjected to solid-liquid separation to remove the first solvent and unreacted catalyst, and then the solid obtained by the solid-liquid separation is washed with the first solvent and dried to obtain the intermediate product D.

[0079] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separation of solids and liquids may be used. For example, the solid-liquid separation may be performed by filtration and / or centrifugation.

[0080] The drying may be performed by a method for removing solvents commonly used in the art. In a preferred embodiment of the present invention, the solvent is removed by vacuum removal at 10-25°C.

[0081] Step 2): In the presence of a second solvent, the intermediate product D is subjected to a second contact reaction with the compound E to obtain the intermediate product D. Intermediate product F .

[0082] In the above step 2), the amount of the compound E can be selected according to the amount of the intermediate product D. Preferably, the molar ratio of the intermediate product D to the compound E is 1:0.9-1.1, more preferably 1:0.95-1.05.

[0083] In the above step 2), the second solvent is one or more of aromatic hydrocarbons, ethers and halogenated alkanes, preferably one or more of diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0084] The amount of the second solvent can be selected according to the intermediate product D. For example, relative to 1 mol of the intermediate product D, the amount of the second solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0085] In the above step 2), the contact method of the second contact reaction is not particularly limited, as long as the intermediate product F can be obtained. Preferably, under an inert atmosphere (for example, it can be carried out under a nitrogen atmosphere or an argon atmosphere), the compound E is dispersed in part of the second solvent, and then a solution in which the intermediate product D is dissolved in another part of the solvent is added dropwise to the solution in which the compound E is dispersed to carry out the second contact reaction.

[0086] Preferably, the operation of dispersing the compound E in part of the second solvent is performed at a temperature of -30 to 0°C, for example, stirring at -20°C for about 30 minutes.

[0087] The conditions of the second contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0088] After the second contact reaction, the product can be purified by conventional purification methods in the art. In a preferred embodiment of the present invention, after the second contact reaction is completed, the product of the second contact reaction is poured into a saturated aqueous solution of ammonium chloride, the organic phase is separated, the aqueous phase is extracted with, for example, ether, the organic phases are combined, dried with a desiccant (for example, anhydrous sodium sulfate), and the organic solvent is removed (for example, the organic solvent is removed in vacuo) to obtain an intermediate product F.

[0089] Step 3): In the presence of a third solvent, the intermediate product F is reacted with M(NA 2 ) 4 The third contact reaction is carried out to obtain Compound H .

[0090] The above M(NA 2 ) 4 In the above, A is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0091] The above M(NA 2 )4 In the above, M is preferably a tetravalent transition metal atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, further preferably a titanium atom or a zirconium atom, and particularly preferably a zirconium atom.

[0092] In the above step 3), M(NA 2 ) 4 The amount of the intermediate product F can be selected according to the amount of the intermediate product F. Preferably, the intermediate product F and M(NA 2 ) 4 The molar ratio is 1:0.95-1.05, more preferably 1:0.98-1.02.

[0093] In the above step 3), the third solvent may be, for example, toluene.

[0094] The amount of the third solvent can be selected according to the intermediate product F. For example, relative to 1 mol of the intermediate product F, the amount of the third solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0095] The conditions of the third contact reaction may include: reacting under reflux for 12-36 hours.

[0096] Preferably, the third contact reaction is carried out under an inert atmosphere, for example, under a nitrogen atmosphere or an argon atmosphere.

[0097] After the third contact reaction, the conventional refining method in the art can be used for purification. In a preferred embodiment of the present invention, after the third contact reaction is completed, the third contact reaction product is cooled and solid-liquid separation is performed, and then the solvent is removed in vacuo to obtain compound H.

[0098] The solid-liquid separation is not particularly limited, and various methods commonly used in the art for separation of solids and liquids may be used. For example, the solid-liquid separation may be performed by filtration and / or centrifugation.

[0099] In the present invention, X 1 and X 2 The method for preparing a metallocene compound containing a halogen atom preferably comprises the following steps:

[0100] 4) in the presence of a fourth solvent, the intermediate product F is subjected to a fourth contact reaction with n-butyl lithium, and the fourth contact reaction product is reacted with MX 4 Carry out the fifth contact reaction to obtain compound I,

[0101]

[0102] MX 4In compound I, X is a halogen atom and M is a tetravalent transition metal atom.

[0103] Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0104] Preferably, M is a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom or a zirconium atom, particularly preferably a zirconium atom.

[0105] As MX 4 Specific examples of the compound include zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide and hafnium tetraiodide, and zirconium tetrachloride is preferred.

[0106] In the above step 4), the fourth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and halogenated alkanes, preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0107] In the above step 4), the amount of the fourth solvent can be selected according to the intermediate product F. For example, relative to 1 mol of the intermediate product F, the amount of the fourth solvent can be 1-30 L, preferably 5-20 L, and more preferably 12-18 L.

[0108] In the above step 4), the fourth contact reaction is preferably carried out by dispersing the intermediate product F in the fourth solvent under an inert atmosphere (for example, it can be carried out under a nitrogen atmosphere or an argon atmosphere), and then dropping an n-butyl lithium solution (for example, an n-butyl lithium hexane solution) into the solution in which the intermediate product F is dispersed to carry out the fourth contact reaction.

[0109] Preferably, the operation of dispersing the intermediate product F in the fourth solvent is performed at a temperature of -30 to 0°C, for example, stirring at -20°C for about 30 minutes.

[0110] The conditions of the fourth contact reaction may include: a temperature of 10-40° C. and a time of 8-40 h.

[0111] In the above step 4), preferably, the molar ratio of the intermediate product F to n-butyl lithium is 1:2-2.4, preferably 1:2.1-2.2.

[0112] In the above step 4), the fourth contact reaction product is reacted with MX 4 A fifth contact reaction is performed, in which MX 4The solvent may be directly added to the fourth contact reaction product in a solid form, or may be used in a dispersed form in a fifth solvent.

[0113] Examples of the fifth solvent include the same solvents as those described above for the fourth solvent.

[0114] In step 4) above, MX 4 The amount of the intermediate product F can be selected according to the intermediate product F. Preferably, the intermediate product F and MX 4 The molar ratio is 1:0.95-1.

[0115] In the above step 4), the fifth contacting method is preferably: in an inert atmosphere (for example, it can be carried out in a nitrogen atmosphere or an argon atmosphere), MX 4 The fifth contact reaction is carried out after the solution is added dropwise to the product of the fourth contact reaction.

[0116] The conditions of the fifth contact reaction may include: temperature of 10-40° C. and time of 8-96 h.

[0117] After the fifth contact reaction, the conventional refining method in the art can be used for refining. In a preferred embodiment of the present invention, after the fifth contact reaction is completed, the fifth contact reaction product is subjected to solid-liquid separation, and the solid obtained by solid-liquid separation is extracted 3-5 times with an organic solvent (preferably toluene), and then the liquid phase obtained by solid-liquid separation is combined with the extract, and the solvent is removed under vacuum and then washed (for example, with n-hexane), and then the residual solvent in the solid is removed under vacuum to obtain compound I.

[0118] In the present invention, the preparation method of compound I can also be such that the second contact reaction product obtained in step 2) above is directly reacted with MX 4 The fifth contact reaction is carried out to obtain compound I.

[0119] In the present invention, X 1 and X 2 The method for preparing a metallocene compound which is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms preferably comprises the following steps:

[0120] 5) in the presence of a sixth solvent, the compound I and R 0 MgY is subjected to a sixth contact reaction to obtain compound J,

[0121]

[0122] R 0 MgY, R 0It is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms; Y is a chlorine atom or a bromine atom.

[0123] The alkyl group having 1 to 10 carbon atoms or the aromatic group having 6 to 12 carbon atoms are as described above.

[0124] In the above step 5), preferably, the compound I and R 0 The molar ratio of MgY is 1:2-3, more preferably 1:2.2-2.5.

[0125] In the above step 5), preferably, the sixth solvent is one or more of alkanes, aromatic hydrocarbons, ethers and halogenated alkanes, more preferably one or more of n-hexane, diethyl ether, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

[0126] The amount of the sixth solvent can be selected according to the compound I. For example, relative to 1 mol of the intermediate product I, the amount of the sixth solvent can be 5-60 L, preferably 10-40 L, and more preferably 25-32 L.

[0127] In the above step 5), the sixth contacting method is preferably: in an inert atmosphere (for example, it can be carried out in a nitrogen atmosphere or an argon atmosphere), R 0 The MgY solution is added dropwise to the mixture of the compound I and the sixth solvent to perform the sixth contact reaction.

[0128] The conditions of the sixth contact reaction may include: a temperature of 10-40° C. and a time of 10-30 h.

[0129] After the sixth contact reaction, the conventional refining method in the art can be used for purification. In a preferred embodiment of the present invention, after the sixth contact reaction is completed, the fifth contact reaction product is subjected to solid-liquid separation, and then the obtained solid is vacuum-dried to remove the solvent to obtain compound J.

[0130] According to a second aspect of the present invention, a catalyst composition is provided, wherein the catalyst composition comprises the following components:

[0131] a) the metallocene compound according to the first aspect of the present invention;

[0132] b) Co-catalyst component.

[0133] According to the catalyst composition of the present invention, preferably, the co-catalyst component comprises a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound; more preferably, the co-catalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.

[0134] The alkylaluminoxane is preferably a compound selected from the group consisting of compounds represented by formula (2) and / or formula (3).

[0135]

[0136]

[0137] In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n is an integer of 4 to 30; more preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n is an integer of 10 to 30.

[0138] Specific examples of the above-mentioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl.

[0139] Examples of n include 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30.

[0140] Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane and the like, and among them, methylaluminoxane is preferred.

[0141] According to the catalyst composition of the present invention, preferably, the organic boron compound is [B(C 6 F 5 ) 4 ] - Z + , Z + Having a structure represented by formula (4) or formula (5),

[0142]

[0143] According to the catalyst composition of the present invention, preferably, the organoaluminum compound is of the general formula AlX 1 X 2 X 3 The compound of the structure shown, X 1 , X 2 and X 3 are respectively a halogen atom or an alkyl group having 1 to 12 carbon atoms, X 1 , X 2 and X 3They may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms.

[0144] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups.

[0145] Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, and particularly preferably chlorine.

[0146] In the present invention, specific examples of the organoaluminum compound include diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, or a mixture of two or more thereof, preferably triisobutylaluminum.

[0147] According to the catalyst composition of the present invention, the co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated on the basis of aluminum is 1:(100-50000), preferably 1:(500-10000), and more preferably 1:(500-2000).

[0148] According to the catalyst composition of the present invention, when the co-catalyst component is a combination of an organic boron compound and an organic aluminum compound, the molar ratio of the metallocene compound to the organic boron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), and the molar ratio of the metallocene compound to the organic aluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

[0149] According to a third aspect of the present invention, there is provided a method for olefin polymerization, wherein the method comprises contacting an olefin with the catalyst composition according to the second aspect of the present invention to carry out a polymerization reaction.

[0150] According to the method of the present invention, preferably, the concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

[0151] According to the method of the present invention, preferably, the polymerization reaction is carried out in an inert organic solvent. As the inert organic solvent, it can be a mixture of one or more of a straight-chain aliphatic hydrocarbon, a branched aliphatic hydrocarbon, a substituted or unsubstituted cyclic aliphatic hydrocarbon, a substituted or unsubstituted aromatic hydrocarbon. As specific examples of the inert organic solvent, hexane, heptane, cyclohexane, cyclooctane, toluene, and xylene can be cited, among which one or more of toluene, cyclohexane and hexane are preferred. In addition, the amount of organic solvent can be determined according to the reaction activity to ensure that the produced polymer is well dissolved in the system, at least without affecting dispersion.

[0152] According to the method of the present invention, preferably, the olefin is ethylene or a combination of ethylene and α-olefin.

[0153] According to the method of the present invention, preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0154] According to the method of the present invention, when the olefin is ethylene, the partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0155] According to the method of the present invention, when the olefin is a combination of ethylene and α-olefin, the amount of ethylene and the α-olefin used can be the usual amount used in the field for synthesizing ethylene-α-olefin copolymers, for example, the α-olefin concentration in the polymerization reaction system is 0.001-8 mol / L, preferably 0.005-4 mol / L. In addition, the partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

[0156] According to the method of the present invention, the polymerization reaction conditions may be the conditions commonly used in the art for synthesizing polyolefins. Preferably, the polymerization reaction temperature is -50 to 200°C, and the polymerization reaction time is 1 to 300 minutes; more preferably, the polymerization reaction temperature is -20 to 150°C, and the polymerization reaction time is 5 to 60 minutes.

[0157] According to a fourth aspect of the present invention, there is provided use of the metallocene compound described in the first aspect of the present invention or the catalyst composition described in the second aspect of the present invention in olefin polymerization.

[0158] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0159] The raw materials used in the following examples and comparative examples, unless otherwise specified, are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0160] In the following examples and comparative examples, the compounds synthesized1 H NMR ( 1 H-NMR) was performed on a Bruker AVANCE III-400 MHz spectrometer with CDCl 3 The reaction was carried out at 25°C as solvent.

[0161] Polymer molecular weights were determined by gel permeation chromatography (GPC) at 150°C with 1,2,4-trichlorobenzene as solvent on a Waters Alliance GPCV2000.

[0162] The comonomer content in the polymer is determined by the solution 13 C NMR ( 13 C-NMR) experiments were performed on a Bruker AVANCE III-400 MHz spectrometer equipped with a 10 mm PASEX 13C-1H / D Z-GRD probe. 13 C resolution was 0.09 Hz. 200 mg of polymer material was dissolved in 2.5 ml of D in a 10 mm test tube at 130 °C. 4 The sample solution was prepared in o-dichlorobenzene (ODCB-d4). 13 C-NMR measurements were performed at 125°C, 20 Hz spin rate, 90° pulse angle, continuous Waltz-16 decoupling, 120 ppm spectral width, 5 s acquisition time, and 10 s relaxation delay. The repeating main chain methylene peak was set to 30.0000 ppm as a chemical shift reference.

[0163] Example 1

[0164] This example is used to illustrate the synthesis of metallocene compound H-1

[0165] Metallocene compound H-1: In the above compound H, M is zirconium, NA 2 It is a dimethylamino group.

[0166] 1) Synthesis of intermediate D

[0167] At 15°C, in a 250 ml three-necked flask with magnetic stirring, add catalyst C (pyrrolidine, 12 mmol) and 30 ml of anhydrous methanol, stir for 5 minutes, add compound A (1.8 g, 11.98 mmol), stir for 5 minutes, add compound B (2.0 g, 30.26 mmol), stir and react for 24 hours, keeping the reaction temperature not higher than 25°C. Filter to remove the solvent and catalyst, and wash the product with anhydrous methanol. Remove the residual solvent in vacuo at room temperature to obtain 2.26 g of yellow solid, with a yield of 94%.

[0168] 1 H-NMR (CDCl3 ): 6.62-6.55ppm(2H), 6.55-6.48ppm(2H), 3.33-3.24ppm(2H), 2.14-1.85ppm(12H).

[0169] 2) Synthesis of intermediate F

[0170] Under nitrogen atmosphere, 344 mg (2.0 mmol) of reactant E (fluorenyl lithium) was dispersed in 30 ml of tetrahydrofuran and stirred at -20°C for 30 minutes; 400 mg of intermediate product D (2.0 mmol) was dissolved in 10 ml of tetrahydrofuran, and the solution was slowly added dropwise to the fluorenyl lithium tetrahydrofuran solution; after the addition, the temperature was slowly raised to room temperature and stirred for 24 hours; the reaction mixture was poured into a saturated aqueous solution of ammonium chloride, the organic phase was separated, the aqueous phase was extracted with ether, the organic phases were combined, dried over anhydrous sodium sulfate, and the organic solvent was removed in vacuo to obtain 622 mg of a yellow solid with a yield of 81%.

[0171] 3) Synthesis of Metallocene Compound H-1

[0172] Under nitrogen atmosphere, 383 mg of intermediate F (1 mmol) was dissolved in 15 ml of toluene, and 267 mg of reactant Zr(NMe 2 ) 4 (1 mmol), refluxed at 110°C for 24 hours, cooled and filtered, the solvent was removed in vacuo to obtain 461 mg of an orange solid, with a yield of 85%.

[0173] 1 H-NMR (CDCl 3 ): 8.25-8.15ppm(2H), 7.83-7.75ppm(2H), 7.65-7.55ppm(2H), 7.23-7.14ppm(2H), 6.43-6.3 5ppm(2H), 5.78-5.70ppm(2H), 2.55-2.51ppm(12H), 2.40-2.25ppm(6H), 2.06-1.88ppm(8H).

[0174] Example 2

[0175] Synthesis of Metallocene Compound I-1

[0176] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0177] Weigh fluorene (499 mg, 3 mmol) into a 250 ml three-necked flask A, replace the vacuum-nitrogen three times, and then add 10 ml of anhydrous ether that has been pre-dehydrated and deoxygenated to dissolve. Place the three-necked flask A in a -20°C oil bath and stir for 15 minutes. At -20°C, add n-butyl lithium (1.05 equivalents, 2.5 mol per liter of hexane solution) dropwise into the three-necked flask A, and after completion, transfer the three-necked flask A to room temperature and stir for 8 hours. Weigh the intermediate product D (631 mg, 1.05 equivalents) into another 100 ml three-necked flask B, replace the nitrogen three times, and then add 10 ml of anhydrous ether that has been pre-treated with dried molecular sieves to dissolve. Place the aforementioned three-necked flask A in a -20°C oil bath and stir for 15 minutes. Add the solution in the three-necked flask B dropwise into the three-necked flask A. After completion, transfer the three-necked flask A to room temperature and stir for 24 hours. The three-necked flask A was placed in a -20°C oil bath and stirred for 15 minutes. N-butyl lithium (1.05 equivalents, 2.5 mol / L hexane solution) was added dropwise to the three-necked flask A. After completion, the three-necked flask A was transferred to room temperature and stirred for 8 hours. The three-necked flask A was placed in a -70°C oil bath and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (700 mg, 3 mmol) solid was added to the three-necked flask A three times and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged (3500 rpm) to take the supernatant, the residual solid was extracted with 5 ml of anhydrous ether, centrifuged (3500 rpm) to take the supernatant, extracted three times in total, and the residual solid was discarded. The supernatant and the extract were combined and the ether was removed under vacuum. The obtained solid was dissolved with a small amount of toluene, filtered into a sample bottle, and an equal volume of ultra-dry n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the sample was centrifuged to obtain 471 mg of solid compound with a yield of 30%.

[0178] 1 H-NMR (CDCl 3 ): 8.23-8.14ppm(2H), 7.79-7.70ppm(2H), 7.63-7.54ppm(2H), 7.24-7.15ppm(2H) , 6.43-6.35ppm (2H), 5.77-5.68ppm (2H), 2.48-2.33ppm (6H), 2.15-1.97ppm (8H).

[0179] Example 3

[0180] Synthesis of Metallocene Compound I-1

[0181] Metallocene compound I-1: In compound I, M is zirconium and X is a chlorine atom.

[0182] Under nitrogen atmosphere, 383 mg of intermediate product F (1 mmol) was dissolved in 15 ml of toluene. At -20 ° C, 0.84 mL of n-butyl lithium (2.5 mol per liter of hexane solution) was added dropwise. After completion, the three-necked flask A was transferred to room temperature and stirred for 8 hours. The three-necked flask A was placed in a -70 ° C oil bath and stirred for 30 minutes. Under nitrogen protection, zirconium tetrachloride (233 mg, 1 mmol) solid was added to the three-necked flask A three times and stirred at room temperature for 72 hours. The reaction mixture was transferred to a centrifuge tube, centrifuged (3500 rpm) to take the supernatant, the residual solid was extracted with 5 ml of anhydrous ether, centrifuged (3500 rpm) to take the supernatant, extracted three times in total, and the residual solid was discarded. The supernatant and the extract were combined and the ether was removed under vacuum. The obtained solid was dissolved in a small amount of toluene, filtered into a sample bottle, and an equal volume of ultra-dry n-hexane was added. After standing in a nitrogen box at room temperature for 24 hours, the sample was centrifuged to obtain 276 mg of solid compound with a yield of 53%.

[0183] The obtained solid compound was confirmed to be the metallocene compound I-1 by nuclear magnetic resonance measurement.

[0184] Example 4

[0185] Synthesis of Metallocene Compound J-1

[0186] Metallocene compound J-1: M is zirconium, R 0 It is benzyl.

[0187] Under nitrogen atmosphere, 525 mg of metallocene compound I (1 mmol) was dissolved in 30 ml of toluene and stirred in a -70°C oil bath for 30 minutes. 2 ml of benzylmagnesium chloride solution (1 mol / L tetrahydrofuran solution) was added dropwise. The temperature was slowly raised to room temperature. The mixture was reacted for 24 hours, filtered, and the solvent was removed in vacuo to obtain 523 mg of an orange-yellow solid with a yield of 82%.

[0188] 1 H-NMR (CDCl 3 ): 8.28-8.20ppm(2H), 7.82-7.74ppm(2H), 7.64-7.53ppm(2H), 7.32-7.08ppm(12H), 6.45-6.38ppm(2H) , 5.77-5.67ppm (2H), 2.62-2.58ppm (4H), 2.55-2.51ppm (12H), 2.41-2.25ppm (6H), 2.09-1.90ppm (8H).

[0189] Example 5

[0190] Synthesis of Metallocene Compound J-2

[0191] Metallocene compound J-2: M is zirconium, R0 It is methyl.

[0192] Under nitrogen atmosphere, 472 mg of metallocene compound I (1 mmol) was dissolved in 30 ml of toluene and stirred in a -70°C oil bath for 30 minutes. 2 ml of methylmagnesium bromide solution (1 mol / L tetrahydrofuran solution) was added dropwise. The temperature was slowly raised to room temperature. The mixture was reacted for 24 hours, filtered, and the solvent was removed in vacuo to obtain 357 mg of an orange-yellow solid with a yield of 74%.

[0193] 1 H-NMR (CDCl 3 ): 8.24-8.15ppm(2H), 7.79-7.71ppm(2H), 7.62-7.54ppm(2H), 7.24-7.16ppm(2H), 6.43-6.35ppm(2 H), 5.77-5.67ppm (2H), 2.55-2.51ppm (12H), 2.40-2.25ppm (6H), 2.06-1.88ppm (8H), -0.97ppm (6H).

[0194] Example 6

[0195] This example is used to illustrate the homopolymerization of ethylene.

[0196] A fully dried 250 ml glass polymerization bottle was evacuated and flushed with nitrogen, and repeated three times. Evacuate, control the electromagnetic valve, fill with ethylene, and heat the oil bath to 70°C to maintain 1 standard atmospheric pressure of ethylene in the polymerization bottle. Add 25 ml of toluene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol triisobutylaluminum), and 2 ml of catalyst toluene solution (containing 5 micromoles of compound I-1) in sequence. After the temperature stabilizes at 70°C, add 2 ml of triphenyl carbon tetrakis (pentafluorophenyl) borate toluene solution (containing 6.0 micromoles triphenyl carbon tetrakis (pentafluorophenyl) borate) and start timing. During the reaction, when ethylene is consumed, add ethylene to keep 1 standard atmospheric pressure of ethylene in the polymerization bottle. After 20 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 0.66 g of polymer with an activity of 396 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=7.8×10 4 , molecular weight distribution MWD=2.07.

[0197] Example 7

[0198] This example is used to illustrate the homopolymerization of ethylene.

[0199] A fully dried 250 ml glass polymerization bottle was evacuated and flushed with nitrogen, and repeated three times. Evacuate, control the electromagnetic valve, fill with ethylene, and heat the oil bath to 70°C to maintain 1 standard atmosphere of ethylene in the polymerization bottle. Add 25 ml of toluene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol triisobutylaluminum), and 2 ml of catalyst toluene solution (containing 5 micromoles of compound I-1) in sequence. After the temperature stabilizes at 70°C, add 2 ml of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate toluene solution (containing 6.0 micromoles of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) and start timing. During the reaction, when ethylene is consumed, add ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 0.79 g of polymer with an activity of 474 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=9.8×10 4 , molecular weight distribution MWD=2.12.

[0200] Example 8

[0201] This example is used to illustrate the homopolymerization of ethylene.

[0202] A fully dried 250 ml glass polymerization bottle was evacuated and flushed with nitrogen, and repeated three times. Evacuate, control the solenoid valve, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. Add 25 ml of toluene and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) in sequence. After the temperature stabilizes at 70°C, add 2 ml of catalyst toluene solution (containing 5 micromoles of compound I-1) and start timing. During the reaction, when ethylene is consumed, add ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, turn off the ethylene, pour the reaction solution into a beaker, add 300 ml of ethanol and 5 ml of concentrated hydrochloric acid, stir for more than 6 hours, filter to obtain a polymer, and vacuum dry at 60°C for 24 hours to obtain 0.71 g of polymer with an activity of 426 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer detected by gel permeation chromatography is Mw=7.9×10 4 , molecular weight distribution MWD=217.

[0203] Example 9

[0204] This example is used to illustrate the homopolymerization of ethylene.

[0205] A fully dried 100 ml stainless steel polymerization kettle was evacuated and flushed with nitrogen three times, and finally filled with ethylene. The heating was set to 75°C. During the heating process, 50 ml of toluene and 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) were added in sequence. After the temperature stabilized at 75°C, 2 ml of catalyst toluene solution (containing 2 micromoles of compound I-1) was added. After 5 minutes, 2 ml of triphenyl carbon tetrakis (pentafluorophenyl) borate toluene solution (containing 2.4 micromoles of triphenyl carbon tetrakis (pentafluorophenyl) borate) was added. The ethylene pressure was quickly increased to 6 standard atmospheres, the heating was set to 80°C, and the timing was started. During the reaction, when ethylene was consumed, ethylene was continuously replenished so that the total pressure in the polymerization bottle was always maintained at 6 standard atmospheres. After 30 minutes, ethylene was turned off, the reaction solution was poured into a beaker, 300 ml of ethanol and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred for more than 6 hours. The polymer was filtered and dried under vacuum at 60°C for 24 hours to obtain 4.980 g of polymer with an activity of 4980 kg polymer / mol catalyst / hour. The weight average molecular weight of the polymer measured by gel permeation chromatography was Mw=17.2×10 4 , molecular weight distribution MWD=2.30.

[0206] Example 10

[0207] This example is used to illustrate the homopolymerization of ethylene.

[0208] The method of Example 8 was followed, except that the same molar amount of compound J-1 was used to replace compound I-1. 0.9 g of polymer was obtained in the same manner, with an activity of 540 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=9.1×10 4 , molecular weight distribution MWD=2.21.

[0209] Embodiment 11

[0210] This example is used to illustrate the homopolymerization of ethylene.

[0211] The method of Example 8 was followed, except that the same molar amount of compound J-2 was used to replace compound I-1. The polymer (1.01 g) was obtained in the same manner, with an activity of 606 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=8.9×10 4 , molecular weight distribution MWD=2.17.

[0212] Comparative Example 1

[0213] A fully dried 250 ml glass polymerization bottle was evacuated and flushed with nitrogen, and repeated three times. Evacuate, control the electromagnetic valve, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. Add 25 ml of toluene and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol methylaluminoxane) in turn. After the temperature stabilizes at 70°C, add 2 ml of catalyst toluene solution (containing 5 micromoles of dichlorodiphenylmethane) and start timing. During the reaction, when ethylene is consumed, replenish ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, turn off the ethylene, pour the reaction solution into a beaker, add 300 ml of ethanol and 5 ml of concentrated hydrochloric acid, stir for more than 6 hours, filter to obtain a polymer, and vacuum dry at 60°C for 24 hours to obtain 0.47 g of polymer with an activity of 282 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer detected by gel permeation chromatography is Mw=2.6×10 4 , molecular weight distribution MWD=1.99.

[0214] Example 12

[0215] This example is used to illustrate the copolymerization of ethylene and 1-hexene.

[0216] A fully dried 250 ml glass polymerization bottle was evacuated and flushed with nitrogen, and repeated three times. Evacuate, control the electromagnetic valve, fill with ethylene, heat the oil bath to 70°C, and keep 1 standard atmosphere of ethylene in the polymerization bottle. Add 24 ml of toluene, 1 ml of 1-hexene, and 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) in sequence. After the temperature stabilizes at 70°C, add 2 ml of catalyst toluene solution (containing 5 micromoles of compound I-1) and start timing. During the reaction, when ethylene is consumed, replenish ethylene to keep 1 standard atmosphere of ethylene in the polymerization bottle. After 20 minutes, turn off the ethylene, pour the reaction solution into a beaker, add 300 ml of ethanol and 5 ml of concentrated hydrochloric acid, stir for more than 6 hours, filter to obtain a polymer, and vacuum dry at 60°C for 24 hours to obtain 1.77 g of polymer with an activity of 1062 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer detected by gel permeation chromatography is Mw=5.1×10 4 , molecular weight distribution MWD=1.91, and the 1-hexene unit content in the polymer was 7.1 mol% as detected by nuclear magnetic resonance carbon-13 spectrum.

[0217] Example 13

[0218] This example is used to illustrate the copolymerization of ethylene and 1-hexene.

[0219] The method of Example 12 was followed, except that the same molar amount of compound H-1 was used to replace compound I-1. The same polymer of 1.51 g was obtained, with an activity of 906 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=3.5×10 4 , molecular weight distribution MWD=1.95, and the 1-hexene unit content in the polymer was 7.1 mol% as detected by nuclear magnetic resonance carbon-13 spectrum.

[0220] Embodiment 14

[0221] This example is used to illustrate the copolymerization of ethylene and 1-hexene.

[0222] The method of Example 12 was followed, except that the same molar amount of compound J-1 was used to replace compound I-1. The same polymer of 1.87 g was obtained, with an activity of 1116 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=3.8×10 4 , molecular weight distribution MWD=1.92, and the 1-hexene unit content in the polymer was 8.0 mol% as detected by nuclear magnetic resonance carbon-13 spectrum.

[0223] Embodiment 15

[0224] This example is used to illustrate the copolymerization of ethylene and 1-hexene.

[0225] The method of Example 12 was followed, except that the same molar amount of compound J-2 was used to replace compound I-1. The same polymer of 2.23 g was obtained, with an activity of 1338 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=4.2×10 4 , molecular weight distribution MWD=1.99, and the 1-hexene unit content in the polymer was 8.5 mol% as detected by nuclear magnetic resonance carbon-13 spectrum.

[0226] Comparative Example 2

[0227] The method of Example 12 was followed, except that the same molar amount of zirconocene dichloride was used to replace compound I-1. 2.12 g of polymer was obtained in the same manner, with an activity of 1272 kg polymer / mol catalyst / hour. The weight-average molecular weight of the polymer measured by gel permeation chromatography was Mw=4.5×10 4 , molecular weight distribution MWD=1.95, and the 1-hexene unit content in the polymer was 8.7 mol% as detected by nuclear magnetic resonance carbon-13 spectrum.

[0228] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A metallocene compound, characterized in that The metallocene compound has a structure shown in formula (1), In formula (1), M is a tetravalent transition metal atom; X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an N,N-dialkylamino group having 2 to 8 carbon atoms.

2. The metallocene compound according to claim 1, wherein M is a titanium atom, a zirconium atom or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a zirconium atom; Preferably, X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or an N,N-dialkylamine group having 2 to 6 carbon atoms; Preferably, X 1 and X 2 Each is independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aromatic group having 6 to 8 carbon atoms, or an N,N-dialkylamino group having 2 to 6 carbon atoms; Preferably, X 1 and X 2 Each is independently F, Cl, Br, I, methyl, ethyl, propyl, phenyl, benzyl, N,N-dimethylamino, N,N-diethylamino or N,N-dipropylamino; Preferably, X 1 and X 2 Each is independently Cl, methyl, benzyl or N,N-dimethylamino.

3. A catalyst composition, characterized in that The catalyst composition comprises the following components, a) the metallocene compound according to claim 1 or 2; b) Co-catalyst component.

4. The catalyst composition according to claim 3, wherein The co-catalyst component includes a combination of an alkylaluminoxane or an organic boron compound and an organic aluminum compound; Preferably, the co-catalyst component is an alkylaluminoxane or a combination of an organic boron compound and an organic aluminum compound.

5. The catalyst composition according to claim 4, wherein The alkylaluminoxane is a compound selected from the group consisting of compounds represented by formula (2) and / or formula (3), In formula (2) and formula (3), R is selected from an alkyl group having 1 to 15 carbon atoms, and n represents an integer of 4 to 30; Preferably, R is selected from an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 10 to 30; Preferably, the alkylaluminoxane is methylaluminoxane.

6. The catalyst composition according to claim 4, wherein The organic boron compound is [B(C6F5)4] - Z + , Z + Having a structure represented by formula (4) or formula (5), 7. The catalyst composition according to claim 4, wherein The organoaluminum compound is a compound having a structure represented by the general formula AlX1X2X3, wherein X1, X2 and X3 are halogen atoms or alkyl groups having 1 to 12 carbon atoms, respectively; X1, X2 and X3 may be the same or different, and at least one of them is an alkyl group having 1 to 12 carbon atoms; Preferably, the organoaluminum compound is one or a mixture of two or more of diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, preferably triisobutylaluminum.

8. The catalyst composition according to claim 4, wherein The co-catalyst component is alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated on the basis of aluminum is 1:(100-50000), preferably 1:(500-10000), and more preferably 1:(500-2000).

9. The catalyst composition according to claim 4, wherein The co-catalyst component is a combination of an organic boron compound and an organic aluminum compound, the molar ratio of the metallocene compound to the organic boron compound is 1:(1-20), preferably 1:(1-5), more preferably 1:(1-2), the molar ratio of the metallocene compound to the organic aluminum compound is 1:(10-5000), preferably 1:(50-1000), more preferably 1:(50-500).

10. An olefin polymerization method, characterized in that: The method comprises contacting olefin with the catalyst composition described in any one of claims 3 to 9 to carry out polymerization reaction.

11. The method according to claim 10, wherein: The concentration of the metallocene compound in the polymerization reaction system is 1×10 -8 mol / L~1×10 -2 mol / L, preferably 1×10 -6 mol / L~1×10 -3 mol / L.

12. The method according to claim 10, wherein: The olefin is ethylene or a combination of ethylene and α-olefin; Preferably, the α-olefin is selected from one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.

13. The method according to claim 12, wherein: The partial pressure of ethylene is 0.1-6 MPa, preferably 0.1-3 MPa.

14. The method according to claim 10, wherein: The polymerization reaction is carried out in the presence of an organic solvent, which is one or more of toluene, cyclohexane and hexane.

15. The method according to any one of claims 10 to 14, wherein: The polymerization reaction temperature is -50 to 200°C, and the polymerization reaction time is 1 to 300 minutes; Preferably, the polymerization reaction temperature is -20 to 150° C., and the polymerization reaction time is 5 to 60 minutes.

16. Use of the metallocene compound according to claim 1 or 2 or the catalyst composition according to any one of claims 3 to 9 in olefin polymerization.

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